Azo dyestuff and its production



Patented Mar. 26, 1935 ITED/ AT Max Albert Kunz, Mannheim,, and Hans Krzikalla "and Walter Limbacher, Ludwigshafen on-the Rhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y.,

a corporation of Delaware No Drawing. Application November 25, 1933,

Serial 1932 5 clai s. (01. 260-86) 5 anyv suitable diazo compounds free from arsenic.

The term diazo compounds is intended toinclude derivatives I of aromatic; mono- I and polyamines in which one or more amino groups are diazotized. The expression an 8-aminoquinoline is meant to includeB-aminoquinoline itself and derivatives thereof. As derivatives of S-aminoquinoline may be mentioned for example 5-methyl-, 5-chloror 5-alkoxy-8-aminoquinolines or 8-aminoquinoline-5-sulphonic acid. The B-aminoquinolines to be used are capable of coupling which property is usually due to the'fa'ct that an orthoor para-position to the aminogroup in the 8- positi'on is unsubstituted. Monoazo, disazo, or polyazo dyestuffs may be prepared in this way. They are capable of being employed for a great variety of purposes, as for example for dyeing leather, wool, cotton, viscose, artificial silk or natural silk or lacquers. Those'of the dyestuffs which contain sulpho groups may be used for preparing lakes; Generally speaking, the dyestuffs derived from B-aminoquinolines having a free para-positionto the amino group or from diazotized ortho-aminophenols may be employed as after-chroming dyestuffs, and they may. also be converted in substance into complex metal compounds by the usual methods.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by weight.

Example 1 17 parts of metan ili c acid are diazotized in the usual manner and the resultingsolution of the diazo' compound is allowed to flow into an ing is obtained. 'If the 'dyestuif be No.l699,800. In GermanyDecember 16,

PATENT "OFFLC E.

aqueous hydrochloric acid solution of 15.8 "parts of S-aminoquinoline. The coupling sets in immediately and is carried to its end by the addi-. I tion of an excess of sodium acetate or pyridine.

The resulting dyestuff, in the form of its sodium example with hydrochloric acid. The dyestuif I dyes wool orange shades; if the dyeing be aftertreated with bi'chromate or if the dyeing'be effected on chrome-mordanted wool a fast brown dyeboiled with a solution of chromium formate a dyestuff is obtained which dyes wool and leather fast brown shades.

Example 2 24.2 parts of 3.4-dichloraniline-6.-sulphonic I acid are diazotized in the usual manner and the resulting solution of the diazo compoundis added to an aqueous hydrochloric acid solution of-1518 parts of 8-aminoquinoline. The coupling. is carried to completion by theaddition of an. excess I of sodium acetate. I A dyestuff is obtained which."

. In order to prepare the'complexcopper com I pound of the dyestuff it'is boiled with copper sul- I phate or tetramino cupric sulphate. In a similar manner other metal compoundaafs'for example iron or nickel compounds, may be prepared] Components which arefsuitable forjthe preparation of further dyestuffs and the color of the dyeings obtainable with thedyestuffs andpf the II chromed dyestuffs are given 'in the following table:- I

Diazo component Coupling component Dyeing being chromed or dyed on chrome-mordanted fibre alter Dyeing Sulphanilic acid 4-Ohloraniline-2-sulphonic acid S-Amino-quinoline. rin

Brown. 0 Yellow-bro Brown.

4-Chloraniline-3-sulphonic acid 3-Chloraniline-6-sulphonic acid 6-Chlor-3-t01uidine-4-sulphonic a m d Yellow-brown. (l n D O.

4-Toluidine-2-sulphonic acid 2-Anisidine-4-sulphonic acid.

dn Brown.

Para-nitraniline-ortho-sulphonio acid o. Bordeaux red.

Naphthionic Mid 2.6.8-Naphthylamine-disulphonic acid.

Red-brown. Brown Yellow-brown. Brown.

Do. Do. Red-brown.

Brown.

Picramic acid Yellow-brown.-."

Metanilic acid 1-Methyl-3-amino-4-1nethoxy-benzene-fi-sulphonic id l-Aminoi-nitrobenzene-2-sulphonic acid. Picramic cid 8 -Aminoquinoline 5 sulphonic acid. 8-An I1inoquinaldine Orange f1 0 8-Aminoquinaldine-5- sulphonic acid.

Brow Yellow-brown.-.

,Emamplecs The=diazocompound preparedirmn i622 pasts of 2.5-dichloraniline is coupledqwith an aqueous solution of 2'7 parts of 8-apiinoquinoline-5-sulv phonic acid sodium salt andithe boupling is :car-

ried' to its end by the additionof an excess of sodium acetate. A dyestui'f is-tobtaine'rl which dyes wool orange shades.

7 Example 4' i138 ,tpar-ts uof .mra-nitraniline are vdiazotized resulting-tsolution of the diazo compound .istaddedl-to aqueous hydrochloric acid solu- 25 ution pf (@1598 t nants eof seaminoquinoline. -A ,dye-

..stuff is obtained which dyes acetate -rsilk red shades of very good fastness to washing and v I whims-may alsothe employed for-coloring cellu- Aose-uester lacquers. 1

Example 6 The tetrazo compoundmbtainable from 40.2 parts of 4.4 -diaminodiphenylurea 3.3-disul- Mosadldfismmmled :with anaqueous hydrocchlm'ic mtssulution of;:31a;6:parts of 8-amino- JAtxiyestuflkis obtained which-dyes silk lbtown .zrshaxles and :which -dyes cotton brown Example -7 1'Jhonic'acid are diazotizeidflin :the usual manner fl ndfthejsolutionobtainedqisallowed to how into an aqueous hydrochloric acid solution of 1713 parts of 8-aminoguinaldine. :rne coupling-begins atonce;an'excess.ofisodiumacetatevis added a iniorder' to complete it. o 'A jdyestufi is obtained fdyeing wool brown shades which by after-treat- "ment "with bichromate turn .to .fast. lied-brown shadesfldyelng's dissimilar shades are obtained by chromeamordanted .wool. The dyestufi may also "he chromed in substance yielding ;a

jcorriplex chromiumucompound whichmayhbenused for dyingwool or'leather.

-- component-an *8 aminoquinoline.

. Example; a

:20.! parts-0t lnmino a -chloro benzene-fi-sulphonic acid are diazotized in the usual manner and the solution obtained is added to an aqueous ihydrochloricracid solution of 17.3 partsof 8- aminoquinaldine, The-couplingis completed by .theradditionzotanzexcess of sodium acetate. A dyestuflis gobtained which goes on wool yield- .ing orange shades (which upon after-treatment \withhbichromatentum to fast brown shades which latter may be-obtained also when chrome-mor- -danteld wool isr'dyed.

What-we-claim;1;is: 1, The process of producing which comprises coupling an 8 -aminoquinoline "containing at'=least" l"position =at' which am coupling may i take place withanearematic diazo compound freeTromarsenic. I

2. A20 dyestufls 'of the-aromatic series "free j' from arsenic and containing as end coupling wherein the azo ,gtoup; is attacheduto the guinoline nucleusfin eitherftheZS- or 'lezposition. a

4. The azo 'dyestufi corresponding ,tothe1for- *mu'la :wherein: thexazo: groupi-is' attached to :the quino "line nucleus' inieither the 5- orfl-iposition.

:5. The azo dyestufi .-'.corresponding' to the forvmula, i' J MAX ALBERT KUNZ. HANS TWALTER LIMBACHER.

azo dyestuffs tenor 

